WO2023104073A1 - Polymère composite dégradable présentant une ductilité élevée et procédé de préparation s'y rapportant - Google Patents

Polymère composite dégradable présentant une ductilité élevée et procédé de préparation s'y rapportant Download PDF

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Publication number
WO2023104073A1
WO2023104073A1 PCT/CN2022/137160 CN2022137160W WO2023104073A1 WO 2023104073 A1 WO2023104073 A1 WO 2023104073A1 CN 2022137160 W CN2022137160 W CN 2022137160W WO 2023104073 A1 WO2023104073 A1 WO 2023104073A1
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Prior art keywords
polymer according
phbv
composite
ppcp
compatibilizer
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PCT/CN2022/137160
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English (en)
Chinese (zh)
Inventor
李洪国
王勋林
闫怡
傅海
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山东联欣环保科技有限公司
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Publication of WO2023104073A1 publication Critical patent/WO2023104073A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Definitions

  • the invention relates to the technical field described in IPC classification number C08L 67/04, in particular to a composite degradable polymer with strong ductility and a preparation method thereof.
  • PHBV poly(3-hydroxybutyrate-3-hydroxyvalerate)
  • PHBV poly(3-hydroxybutyrate-3-hydroxyvalerate)
  • PHBV is a biodegradable material obtained by microbial fermentation. It has excellent biocompatibility and biodegradability. It is used in medical treatment, food packaging, film Materials, skin care products, manufacturing and other industries have broad application prospects.
  • PHBV has high crystallinity, brittleness, poor ductility and impact resistance, and these problems have also become factors that limit the further application of PHBV.
  • Chinese patent CN109593333A discloses a polylactic acid/PHBV composite material, which reduces the crystallinity of PHBV, increases the elongation at break and glass transition temperature, but reduces the breaking strength.
  • Chinese patent CN105879111A discloses a porous PHBV/PPC composite medical stent, and the toughness of the medical stent is improved by adding PPC.
  • PPC carbon dioxide copolymer
  • PPC has good toughness and mechanical strength, but PPC has a low glass transition temperature and poor thermal stability.
  • the applicant has proposed a composite degradable polymer with strong ductility and a preparation method thereof, using PHBV and PPCP (propylene glycol phthalate-propylene carbonate copolymer) as main raw materials, through melt blending Methods A biodegradable polymer with strong ductility, impact resistance and good thermal stability was obtained.
  • PHBV and PPCP propylene glycol phthalate-propylene carbonate copolymer
  • the purpose of the present invention is to provide a composite degradable polymer with strong ductility, and the preparation raw materials include PHBV, PPCP, compatibilizer and functional auxiliary agent.
  • PPCP is purchased from Shandong Lianchuang Polymer Co., Ltd., and is prepared by polymerization of phthalic anhydride, carbon dioxide, and propylene oxide. Compared with PPC, PPCP has a higher glass transition temperature and tensile strength, and PPCP also has a good Transparency, gas barrier and biodegradability.
  • the elongation at break of the PHBV is 2%.
  • PHBV was purchased from Ningbo Tianan Biomaterials Co., Ltd.
  • the mass ratio of PPCP to PHBV is (1-99): (99-1).
  • the mass ratio of PPCP to PHBV is (20-60): (80-40).
  • the compatibilizer is 0.1-20% of the total weight of PHBV and PPCP.
  • the compatibilizer is a reactive compatibilizer, more preferably, the reactive compatibilizer is selected from maleic anhydride graft copolymers, epoxy compound chain extension compatibilizers , isocyanate chain extension compatibilizer, oxazoline type chain extension compatibilizer, acetyl triethyl citrate, polyvinyl acetate, epoxy styrene-acrylic acid copolymer, etc. or a combination of several.
  • the isocyanate functional group of the isocyanate chain extension compatibilizer is ⁇ 2, more preferably, the isocyanate chain extension compatibilizer is selected from toluene diisocyanate, isophorone diisocyanate, diisocyanate One or a combination of cyclohexylmethane diisocyanate, hexamethylene diisocyanate and triphenylmethane triisocyanate.
  • the isocyanate chain extension compatibilizer is isophorone diisocyanate.
  • the compatibilizer is 0.1-5% of the total weight of PHBV and PPCP.
  • the functional additive is 0.1-15% of the total weight of PHBV and PPCP.
  • the functional additive is 0.1-3% of the total weight of PHBV and PPCP.
  • the functional auxiliary agent is selected from one or a combination of stabilizers, antioxidants, mold release agents, lubricants, fillers and the like.
  • the functional auxiliary agent is a stabilizer, a release agent and an antioxidant.
  • the mass ratio of the stabilizer, release agent and antioxidant is 1:(0.1-0.3):(0.1-0.3).
  • the stabilizer is selected from the group consisting of maleic anhydride, epoxidized soybean oil, isooctyl dimethyl tin dithioacetate, inorganic mineral powder, metal oxide, metal soap one or a combination of several.
  • the stabilizer is maleic anhydride and isooctyl dimethyl tin dithioacetate.
  • the mass ratio of maleic anhydride to isooctyl dimethyltin dithioacetate is 1:(0.2-0.5).
  • the release agent is selected from the group consisting of ethylene bis stearamide, stearate, siloxane compounds, glycerin, polyethylene wax, polyethylene, paraffin, fatty acid, vaseline at least one.
  • the release agent is stearate, more preferably, the stearate is zinc stearate.
  • the antioxidant is selected from N,N'-diphenyl-p-phenylenediamine, alkylated diphenylamine, 2,2'-methylenebis(4-methyl- 6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), benzotriazole, 2-mercaptobenzothiazole, dialkyldithiophosphoric acid One or a combination of zinc.
  • the antioxidant is 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 4,4'-thiobis(6-tert Butyl-3-methylphenol) combination.
  • the 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 4,4'-thiobis(6-tert-butyl-3 - methyl phenol) mass ratio is 1: (1 ⁇ 1.5).
  • the preparation raw materials include, by weight parts, 1-99 parts of PHBV, 1-99 parts of PPCP, 0.1-20 parts of compatibilizer, and 0.1-15 parts of functional additives.
  • the preparation raw materials include, in parts by weight, 40-80 parts of PHBV, 20-60 parts of PPCP, 0.1-5 parts of compatibilizer, and 0.1-3 parts of functional additives.
  • the second aspect of the present invention proposes a method for preparing a composite degradable polymer with strong ductility, comprising the following steps:
  • step (3) Add the mixture obtained in step (2) into a twin-screw extruder, extrude and granulate at 100-180° C. to obtain PPCP/PHBV polymer.
  • the present invention has the beneficial effects:
  • the composite degradable polymer prepared by the present invention improves the mechanical properties such as tensile strength and impact strength of the composite degradable polymer by regulating the addition ratio of PPCP and PHBV, and then combines a specific compatibilizer, isophorone diisocyanate , improve the compatibility of the polymer, and further improve the mechanical properties, thermal stability and photoaging resistance of the polymer.
  • the composite degradable polymer of the present invention has added a specific antioxidant to further reduce the aging rate of the polymer by reducing the generation of free radicals and decomposing hydroperoxides.
  • the polymer of the present application is used in each Under the synergistic effect of a specific raw material, the crystallization degree of the composite copolymer is reduced, the toughness of the composite copolymer is improved, the production cost is reduced, and the application of the composite copolymer in films, sheets, injection molding products and foamed products is improved, and it is suitable for large Large-scale industrial production.
  • the first aspect of this embodiment proposes a composite degradable polymer with strong ductility.
  • the preparation raw materials include 70 parts of PHBV, 30 parts of PPCP, 0.5 part of isophorone diisocyanate, and 1 part of functional additives.
  • the elongation at break of the PHBV is 2%, purchased from Ningbo Tianan Biomaterials Co., Ltd.
  • the PPCP was purchased from Shandong Lianchuang Polymer Co., Ltd.
  • the functional auxiliary agent is a stabilizer, a release agent, and an antioxidant, and the mass ratio is 1:0.3:0.2.
  • the stabilizer is maleic anhydride and isooctyl dimethyltin dithioacetate with a mass ratio of 1:0.3.
  • Described release agent is zinc stearate.
  • the antioxidant is 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 4,4'-thiobis(6-tert-butyl-3-methylphenol) , the mass ratio is 1:1.5.
  • the second aspect of this embodiment proposes a method for preparing a composite degradable polymer with strong ductility, comprising the following steps:
  • step 2 (3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 140° C. to obtain PPCP/PHBV polymer.
  • the first aspect of this embodiment proposes a composite degradable polymer with strong ductility, and the preparation raw materials include 60 parts of PHBV, 40 parts of PPCP, 2 parts of isophorone diisocyanate, and 1.5 parts of functional additives.
  • the elongation at break of the PHBV is 2%, purchased from Ningbo Tianan Biomaterials Co., Ltd.
  • the PPCP was purchased from Shandong Lianchuang Polymer Co., Ltd.
  • the functional auxiliary agent is a stabilizer, a release agent, and an antioxidant, and the mass ratio is 1:0.3:0.2.
  • the stabilizer is maleic anhydride and isooctyl dimethyltin dithioacetate with a mass ratio of 1:0.3.
  • Described release agent is zinc stearate.
  • the antioxidant is 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 4,4'-thiobis(6-tert-butyl-3-methylphenol) , the mass ratio is 1:1.5.
  • the second aspect of present embodiment proposes a kind of preparation method of the composite degradation polymer with strong ductility, comprises the following steps:
  • step 2 (3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 140° C. to obtain PPCP/PHBV polymer.
  • the first aspect of this embodiment proposes a composite degradable polymer with strong ductility
  • the second aspect of this embodiment proposes a method for preparing a composite degradable polymer with strong ductility.
  • the preparation raw materials and specific implementation methods are the same Example 1, the difference is that 1.5 parts of isophorone diisocyanate is added.
  • the first aspect of this embodiment proposes a composite degradable polymer with strong ductility
  • the second aspect of this embodiment proposes a method for preparing a composite degradable polymer with strong ductility.
  • the preparation raw materials and specific implementation methods are the same Example 1, the difference is that 50 parts of PHBV, 50 parts of PPCP, and 1 part of isophorone diisocyanate are added.
  • the first aspect of this embodiment proposes a composite degradable polymer with strong ductility
  • the second aspect of this embodiment proposes a method for preparing a composite degradable polymer with strong ductility.
  • the preparation raw materials and specific implementation methods are the same Embodiment 1, the difference is that the compatibilizer is hexamethylene diisocyanate, and the stabilizer is isooctyl dimethyl tin dithioacetate.
  • the composite degradable polymer prepared in the embodiment was tested for tensile strength, impact strength and biodegradability. The test results are recorded in Table 1.
  • Tensile strength refer to the national standard GB/T1040.
  • Impact strength refer to the national standard GB/T1843-2008.
  • Biodegradability Test with reference to the national standard GB/T19277. The test environment temperature is 58 ⁇ 2°C and the polymer is completely degraded when composting is carried out.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un polymère composite dégradable présentant une ductilité élevée et procédé de préparation s'y rapportant. Le polymère composite dégradable est préparé à partir des matières premières suivantes en parties en poids : 1 à 99 parties de PHBV, 1 à 99 parties de PPCP, 0,1 à 20 parties d'un agent de compatibilité et 0,1 à 15 parties d'un additif fonctionnel. Selon le polymère composite dégradable de la présente invention, en ajustant le rapport d'addition de PPCP à PHBV et en combinant un agent de compatibilité spécifique et une pluralité d'additifs fonctionnels spécifiques, les coûts de production sont réduits, le degré de cristallisation d'un copolymère composite est réduit, des propriétés mécaniques du polymère composite dégradable sont améliorées, la compatibilité du polymère et la stabilité thermique et la capacité anti-photovieillissement du polymère sont améliorées, des applications du copolymère composite dans des films minces, des feuilles, des produits moulés par injection et des produits en mousse sont augmentées et le polymère composite dégradable de la présente invention est adapté à une production industrielle à grande échelle.
PCT/CN2022/137160 2021-12-08 2022-12-07 Polymère composite dégradable présentant une ductilité élevée et procédé de préparation s'y rapportant WO2023104073A1 (fr)

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CN202111490848.3A CN114763430A (zh) 2021-12-08 2021-12-08 一种延展性强的复合降解聚合物及其制备方法
CN202111490848.3 2021-12-08

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Publication number Priority date Publication date Assignee Title
CN117165039A (zh) * 2021-12-07 2023-12-05 山东联欣环保科技有限公司 一种生物降解组合物及其制备方法和应用
CN114763430A (zh) * 2021-12-08 2022-07-19 山东联欣环保科技有限公司 一种延展性强的复合降解聚合物及其制备方法
CN115892736A (zh) * 2022-11-07 2023-04-04 山东联欣环保科技有限公司 一种可生物降解的纸塑复合膜及其制备方法和应用

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